Preparation of hexachlorethane



Patented May 4, 1948 2,440,731 PBEPABATIOIQ OF HEXACHLOBETHANE William H. Vining and Oliver w. Cass, Niagara Falls, N. Y., assignors to E. I. du Pont de Nemom a Company, Wilmington, Del., a corporation of Delaware No Drawing. annucstiona'nne 25. 1943, Serial No. 492,324 I 3 Claims. (Cl. tot-#163) 1 This invention relates to the preparation of halogenated hydrocarbons of higher halogen content by the halogenatlon of halogenated hydrocarbons of lower halogen content. More particulariy, it relates to the manufacture of hexachlor- 5 when subjected to heating. 1 ethane, 02016, by reacting chlorine with perchlor- This process, while satisfactory for the proethylene (also referred to as tetrachlorethylene) duction of relatively small amounts of hexachlor- CnCli, under controlled conditions permitting subethane. was open to a number of objections. stantially complete reaction of the perchlor- Among these was the difllculty of recovering the ethylene starting material and ready recovery of product from the unreacted liquid perchlorthe product. ethylene and the complexity of the apparatus re- Hexachlorethane has previously been prepared quired for economical operation. Not only did from various hydrocarbon and chlorinated hydrofiltration or centrifuging of the hexachlorethane carbon starting materials. It has been prepared product from the liquid perchlorethylene in from chlorohydrocarbons of the methane and which it was suspended involve considerable diffiethane series; from the former by high temculty, but because of the low subliming temperaperature chlorination and pyrolysis and from the ture of hexachlorethane it was practically imlatter by complete chlorination under a wide possible to dry the product at the elevated temvariety of conditions. Moreover hexachlorethane, peratures requisite for rapid drying without extogether with other chlorinated hydrocarbons, cessive losses by sublimation. The process as has been prepared by high temperature chlorinacommercially perated pr v t t, only 11 tion of a number of hydrocarbon and chloroslow and difllcultly controllable batohwise process hydrocarbon starting materials containing more for preparing hexachlorethane. than two carbon atoms. We have now discovered that hexachlorethane One of the processes previously utilized on the can be prepared directly by the chlorination of industrial scale involved reacting perchlorperchlorethylene in a simple, easily controlled, ethylene and chlorine. Unfortunately this flexible process which permits the complete process as carried out under the conditions chlorination of the total amount of suppli p ordinarily utilized industrially has been unsatischlorethylene in a sin l p r n The hexafactory for a number of reasons. Passage of chlorethane productisreadily recovered from the gaseous chlorine into liquid perchlorethylene at reaction mixture without difiiculty and in quantia temperature below its boiling point 021C.) tatlve yields. By reacting perchlorethylene with results in the formation of hexachlorethane in liquid chlflrin n the Presence of n exce s the liquid perchlorethylene which, as its solubility amount of liquid chlorine t as b n o d that in the liquid is exceeded. begins to crystallize out the p rchlor thyl ne can b complet ly chloriof the reaction mixture. If chlorination is conhated in a single operation, the resulting hexatinued in an attempt to convert all or substanchlorethane, which remains suspended in the tially all of the perchlorethylene initially present excess chlorine. bein readily secured in crystalto hexachlorethane there very quickly results a line form simply by vaporizing oil the excess thick viscous mass which cannot be stirred and amount of chlorine. Thus, instead of being faced from which the hexachlorethane cannot be conwith the necessity of drying the product by veniently recovered by any practical method. eliminating an adhering, high-boiling liquid, as In an effort to avoid the formation of too thick in the presently available methods wherein the a slurry and to permit recovery of the product hexachlorethane mustbe freed from adhering from the apparatus gaseous chlorine has been fed perchloret yle e at elat vely high temperatures. into the liquid perchlorethylene only to that in the new method the hexachlorethane is freed point, prior to complete chlorination of all from a low-boiling liquid (liquid chlorine), perchlorethylene present, at which the slurry whereby dry product may be secured by the use could still be actively handled. Then before the of r lativ ly l w t p ratu s at which hexareaction mixture had become too viscous it, was chlorethane has no tendency to sublime. dropped into a crystallizing kettle and the While the boiling point of liquid chlorine at crystalline hexachlorethane separated from the atmospheric pressure is approximately -35-C., cooled liquid by filtration or centrifuging. In the boiling point of our reaction mixture comorder to secure a salable product the hexachlora prising a solution of perchlorethylene in liquid ethane had to be dried to free it from residual point of liquid perchlorethylene and the low temperature at which hexachlorethane sublimes chlorine is somewhat higher, and it is usually 3 possible to carry out the reaction at temperatures within the range -l5 C. to -30 0., without maintaining the reaction mixture under superatmospheric pressure. It is generally preferred,

It is accordingly one of the objects ofthis invention to provide an improved process for the manuiacture of hexachlorethane by reacting perchlorethylene and chlorine under conditions wherein the perchlorethylene can be converted in quantitative amounts to hexachlorethane in a single stage process, thus eliminating the necessity, characteristic of previous processes, or stopping the chlorination when only part of the perchlorethy-lene has been converted. Another object of this invention is to provide a process for the manufacture of hexachlorethane wherein the formed product will remain suspended in crystalline form in an excess amount of liquid chlorine, whereby the hexachlorethane may be readily recovered in crystalline form simply by volatilizing off the excess amount Of liquid chlorine. Still another object of this invention is to provide operating conditions such that both reagents are present in the reaction chamber in maximum amounts, since liquid chlorine and perchlorethylene are miscible in all proportions at the temperatures at which the reaction is carried out, whereby the speed of the reaction is limited only by the rapidity with which the evolved heat can be removed.

Among other objects of our invention is that of providing a process wherein iron equipment can be utilized, since iron is not corroded appreciably by the reagents at the temperatures at which the reaction is carried out, whereas in the previous high temperature methods iron equipment could not be utilized and some more resistant material of construction, suchas lead, or enamel-lined steel, had to be employed. As a further object there may be enumerated the pro- .vision of a process wherein the hexachlorethane is dried at low temperatures, temperatures below those at which serious losses by sublimation occur, from a low boiling adhering liquid, as contrasted with previous methods wherein it was necessary to dry the perchlorethylene at higher temperatures from a relatively high boiling liquid. These and still further objects of our invention will be apparent from the ensuing disclosure whereby hexachlorethane may be prepared by a direct and uncomplicated process requiring a minimum number of procedural steps.

Essentially the process involves adding perchlorethylene, either in one charge or intermittently in successive increments over a period of time, to a body of liquid chlorine maintained at temperatures below 60 C. while the contents of the reaction vessel are agitated and irradiated. The equipment utilized is ordinary steel or iron equipment. The heat evolved, as the reaction is exothermic in character, is removed by allowing chlorine to be vaporized, condensed, and re- 4 turned to the reaction vessel. This is readily accomplished by utilizing apparatus provided with a reflux condenser. When the reaction is complete and all perchlorethylene present has been converted to hexachlorethane the. excess chlorine is vaporized out of the reaction vessel leaving behind pure dry hexachlorethane in substantially quantitative yields.

The process may be operated either continuously or in batch operations. Both the perchlorethylene and liquid chlorine, in total amounts supplied can be added to the reaction vessel at the beginning of the operations, or the perchlorethylene may be added in successive small increments throughout the reaction period. In the first case the heat is developed all at onceand the cooling of the reaction mixture by refluxing the liquid chlorine may present some difllculties, although cooling by reflux may be augmented by additional cooling or the reaction vessel if necessary. When the perchlorethylene is added continuously over the reaction period as used up by reaction with the chlorine it is ordinarily somewhat easier to control the temperature. Irradiation is preferably provided by means of an ordinary electric light bulb, and at the beginning of operations the lights may be operated at reduced brilliancy and turned on to full brilliancy after thirty minutes or when there is evidence that the reaction has begun. Once the reaction is fairly under way the lights need not be operated at full brilliancyand can be operated at reduced brilliancy in order to prevent the reaction from becoming too violent. As the reaction proceeds and the temperature tends to drop it may be necessary to increase the amount of irradiation by operating the light source at full brilliancy, and completiomoi the reaction is generally indicated by rapid decline in temperature even with full light brilliancy. In order to insure complete reaction of perchlorethylene present it has been found advantageous to permit the reaction to continue for at least one hour after the appearance of this temperature drop. The reaction is ordinarily substantially complete at the end of about three to seven hours, although it may be advantageous to continue irradiation for a somewhat longer period, periods 01 over twelve hours being generally unnecessary.

Any pressure-resistant apparatus may be utilized, but very satisfactory results have been secured by the use of a jacketed steel reaction vessel having a conical bottom, which vessel is equipped with an agitator. There should also be provided means for charging the reactants into the vessel under pressure, and means for cooling or heating the Jacket with water or steam. In typical apparatus with which we have secured satisfactory results the top of the reaction vessel is surmounted by a condenser oi the tube and shell type for refluxing the chlorine and thus cooling the reaction mixture so as to prevent the temperature rise and pressureirom becoming excessive. A well, conveniently constructed out 'of a borosilicate glass of low alkali content, containing no elements of the magnesia-lime-zinc group and no heavy metals, is provided in the apparatus in which ordinary tungsten filament lamps may be introduced for the purpose of irradiating the reaction mixture through the glass. As previousiy stated means for controlling the brilliancy of the light and thus the. intensity of the radiation are advantageously provided. A thermometer well in which there may be positioned a thermometer for the purpose of observing temperatures throughout the reaction, together with suitable measuring devices, are also part of the jacketed steel reaction vessel. It should be and that .while this type of apparatus has been found emcient, any other suitable form of apparatus may be utilized, it being only necessary that the perchlorethylene be reacted with liquid chlorine in an excess amount of liquid chlorine at a temperature below about 60 C. and above the temperature, -35 0., at which chlorine exists as a liquid at atmospheric pressure.

The ratio of liquid chlorine to perchlorethylene may vary within considerable limits although we have generally found it advisable to have the liquid chlorine present in at least 100% excess over that amount theoretically necessary to react with the cunt of perchlorethylene present or introduced during the course of the reaction. This amount of excess chlorine sumces to maintain the reaction mass as a readily stirred slurry at the coletion of the reaction.

At the conclusion of the reaction the excess chlorine may be readily removed from the crystalline hexachlorethane product suspended therein by vaporizing the excess chlorine through the condenser and condensing and collecting the chlorine in a suitable receiver. During this process, no difficulty is encountered in stirring the reaction mass, as the hexachlorethane separates as a free flowing crystalline powder. The pressure within the reaction vessel, when the reaction is carried out under pressure to permit the use of temperatures more elevated than about 15 (7., drops during vaporization of the excess chlorine, and part of the chlorine in the reactor may be blown out to the atmosphere, or through a caustic scrubbing system of suitable type. If desired, a current of dry air or partial vacuum 'means may be applied for removing the last traces of chlorine. The resulting product has been found of satisfactory color and chemical composition and, in all respects, meets all commercial standards for hexachlorethane.

The following examples are illustrative of our process:

Example I A pressure-resistant, iron reaction vessel, equipped with stirrer and reflux condenser of the tube and shell type, was charged with 100 lbs. of liquid chlorine and 30 lbs. of perchlorethylene. Upon irradiation of the charge with the light from a tungsten filament lamp positioned in a glass well the reaction began and was complete at the end of approximately 5% hours. The glass well was constructed of a borosilicate glass of low alkali content, containing no elements of the magnesia-lime-zinc group and no heavy metals. After recovering the dry hexachlorethane from unreacted chlorine there was obtained 43 lbs. of product, constituting a yield of substantially 100%. The product was crystalline in character, of satisfactory light color, and exhibited no tendency to cake on storage.

The maximum temperature attained by the reaction mixture during the reaction was 44 0., and the maximum pressure was 74 lbs. per square inch. The reaction mixture was cooled to a satisfactory extent by refluxing part of the liquid chlorine.

Example II A round-bottomed desk was charged with 2840 parts of perchlorethylene. Reaction vessel was then cooled down below the boiling point of chicrine (-35 C.) at atmospheric pressure, whereratus was operated in the bottom of the flask,

and at the end of six hours the reaction was complete. The temperature during the reaction was 17 C. or below.

The dry hexachlorethane was recovered from unreacted chlorine and constituted a yield of approximately 94% of the theoretical. The product was crystalline in character, of satisfactory light color, and exhibited no tendency to cake during storage.

, Example III A one gallon iron pot provided with an eflicient condenser for refluxing liquid chlorine was charged with 2840 parts of perchlorethylene. The pot was cooled to within the range 26 to 32 0., whereupon 3316 parts of liquid chlorine was added to the perchlorethylene. The charge was irradiated by the light from a 40 watt incandescent bulb. An iron stirrer positioned in the bottom of the pot was operated and, at the end of approximately five hours, the reaction was complete.

The hexachlorethane was recovered in the form of a very white crystalline solid simply by permitting the excess of liquid chlorine to evaporate off, followed by subjecting the hexachlorethane to air drying. The yield was approximately 97% and the product, although prepared in iron equipment was free from any appreciable amounts of metal. The product melted at 185.1 C. and was in all respects pure and commercially acceptable.

It is to be understood that the present invention is not to be limited to the particular details above-described, since obvious modifications of these details will occur to a person skilled in the art.

We claim:

1. The process of manufacturing hexachlorethane which comprises bringing together perchlorethylene andliquid chlorine in the presence of light as the catalyst at a temperature below 60 C., the quantity of perchlorethylene present being not'to exceed one-half the 'stoichiometric proportion for the formation of hexachlorethane, and maintaining said reactants in the liquid phase and in contact with each other until substantially all of said perchlorethylene has reacted with chlorine to form hexachlorethane.

2. The process of manufacturing hexachlorethane which comprises bringing together perchlore'thylene and liquid chlorine in the presence of light as the catalyst at a temperature between 35 C. and 60 C.. the quantity of perchlorethylene present being not to exceed one-half the stoichiometric proportion for the formation of hexachlorethane, and maintaining said reactents in the liquid phase and in contact with each other until substantially all of said perchlorethylene has reacted with chlorine to form hexachlorethane.

3. The process of manufacturing hexachlorethane which comprises bringing together perchlorethylene and liquid chlorine in the presence of light as the catalyst at a temperature below 60 0., and at superatmospheric pressure, the quantity of perchlorethylene present being not 8 to exceed one-half the stoichiometric proportion for the formation of hexachlorethane. and mainc a g t-aining said reactants in the' liquid phase andin Bender 1935 contactwith each other until substantially all 2o37419 Levine 1; 1936 of said perchlorethylene has reacted with 2147577 Hass at a] 1939 mm hexachmethane- 2:174:13: Coleman ei 35:11:. on a: 1939 g fi'g 2,200,254 Bender May 14, 1940 2?,255 Bender May 14, 1940 m 2 6,951 Fisher Mar. 17. 1942 REFERENCES 2,296,614 Hearne Sept, 22, 1942 The following references are of record in the file of thi patent; OTHER. REFERENCES UNITED STATES PATENTS am i ie. 1:11. an: 535 an 53;

an Enzinee n: emis ry, arc Number Name Date I 193 pages 33 339 1,315,542 Curme Sept. 9. 1919 

